Chemistry and Technology of Fuels and Oils, Vol. 32, No. 1.

1996

CALCULATION REFORMING

OF MATERIAL

BALANCE FOR CATALYTIC

OF NAPHTHA

FRACTIONS UDC 542.973:66.092.4

E. N. Sudakov

The reforming of 85-180~ naphtha cuts is an important part of the processing plan in modern refineries. The process operates at a pressure of 0.5-4 MPa, temperature 440-515~ feedstock space velocity 1-3 h -1 , and hydrogen-rich gas (HRG) circulation ratio 90-2500 m3/m 3. The content of hydrogen in the HRG is 85-93 % by volume. Kinetic models of reforming are developed on the basis of certain schemes of hydrocarbon conversion. However, such models are unsuitable for engineering calculations, as the models of the elementary reactions are extremely unwieldy. Some kinetic schemes that have been described are based on four to eight stoichiometric equations for reactions of hydrocarbon groups [i, p. 337]. Such large numbers of reactions are used so that the contents of individual aromatic hydrocarbons in the reformer products can be defined more precisely. It is also possible to use simplified kinetic schemes, thanks to a method that has been proposed for converting hydrocarbon-group composition to individual hydrocarbon composition [2]. Let us examine a kinetic scheme that includes four reactions [3, p. 253]: Conversion of naphthenes to aromatics C H~ ~ C.Hz,_,+ 31 ~ Conversion of naphthenes to paraffins C.I-I~ + H2~ C.H~+2 Hydrocracking of naphthenes C.H~. + 3 Hydrocracking of paraffins n-3 n C.Hz.~ + ~ H~~ ~ C.Hz.~ where n = 1-5 is the number of carbon atoms [3, p. 256]. The decreases in quantities of hydrocarbons are described by the differential equations
- a~{av. = _ k~ 3 (5)

(1)

(2)

(3)

(4)

k~Pn kelP,P~: k~ - dNn2/d% = k2PnP, h - ~ P p - dNn3/dv ~ = k~ p~ p

-

(6)

(7)
(8)

dNp ~dr,

k, eP P

M. D. Millionshchikov Grozny Petroleum Institute. Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 1, pp. 20-21, January-February, 1996. 14 0009-3092/96/3201-0014515.00 e1996 Plenum Publishing Corporation

30 21) 9 ~

1 0 - - - ~a 8 6 - -

?
5/..
1.35 1,4

2!
1

/ . -'r

S
/

1,25

1,3

(1/'1")103, K "'

Fig. 1. Rate constant k 1 as a function of reciprocal process temperature 1/T in reforming naphtha fraction over the following catalysts: 1) AP-64; 2) KR-108; 3) KR-110; 4) RB-I; 5) data from [5]. t0oo 4 / ~

~,
20 ~
,

~.
~
0,1

'

1.25

1.3

1,35

1,4

1,25

1,3

1,35

1,4

(I,t1310~, K"
Fig. 2

(1/7)103, K -I
Fig. 3

Fig. 2. Rate constant k2 as a function of reciprocal process temperature 1/T in reforming naphtha cut over various catalysts; see Fig. 1 for notation. Fig. 3. Rate constants k 3 (1-5) and k 4 (1 '-5') as functions of reciprocal process temperature l/Tin reforming naphtha cut over the following catalysts: 1,1') AP-64; 2,2') KR-108; 3,3') KR-110; 4,4') RB-1; 5,5') data from [5]. where Nni and Np are the respective fractions of naphthenic and paraffinic hydrocarbons in the feed that are subjected to conversion through reactions (1)-(4) kmoles/kmole; vR is the reciprocal of the feedstock mass velocity, kg catalyst/(kmoles feed/h); k I is the rate constant of reaction (i), kmoles/(h.Pa.kg catalyst); Pn, Pa, Pp, and pH 2 are the respective partial 15

TABLE 1 i Limits o f HRG Pressure temper- Feedstock space circulain system ature in velocity, tion ratio, t, - l0T, p, MPa system, h- 1 m3/m3 kmoles ~ h-Pa-kg Reaction rate constant kz 9 10 IJ, kmoles h.pa2.kg
k3, k4,

kmoles h'kg

kmoles h.kg

Reforming over indicated catalysts AP-64

3,43 410-510 1,5 1800 3,875 3,427 57,10 96,81 53'75 100,40 43'45 50,73 138,90 651,50 29,60 44,10 10,93 13,96 1,2011 0,0782

KR-108
2,50 1,50 1,50 460-510 445-505 470-515 1,5 1,5 1,5 1200 1200 2500 2,530 2,461 2'455 2,429 2,475 2,467 2p012 1,942 RB-1 2,0 437-495 1,22. 1200 1,274 1,220 0,2554 0,1580 0,6287 0,3782 0,4266 0,2294 0,2828 0,1775

KR-110
2,2 448-498 1,5 1075 0,4833 0,2128

Note. Value in numerator is for lower limit of temperature; value In denominator for upper limit.

pressures of naphthenes, aromatics, paraffins, and hydrogen, Pa; kel is the chemical equilibrium constant of reaction (1), Pa3; k2 is the rate constant of reaction (2), kmole/(h'Pa 2. kg catalyst); ke2 is the chemical equilibrium constant of reaction (2), Pa-1; k 3 and k 4 are the rate constants of reactions (3) and (4), kmoles/(h.kg catalyst); p is the pressure (average) in the system, Pa. The influence of the catalyst on the course of the process is not taken into account in explicit form in Eqs. (5)-(8). The mechanism of reactions (1)-(4) is complex, involving the participation of active intermediate species and the catalyst; the constants kl-k 4 are effective constants [4, p. 32]. In order to account for the influence of various catalysts on the reforming of naphtha cuts, numerical values of these rate constants must be known. After integrating and transforming Eqs. (5)-(8), we obtain Jcl= t" N~nl 1 3 "~ (9)

v,!Pn- ~ P , P . , )
ks-

Nn2 v,(pnp.z _ ~ee2 ) k3=Nn3/V, Pn k4=Np/VRPp

(10) (11)

(12)

In order to perform calculations based on Eqs. (9)-(12), information is needed on the charging rate and feedstock space velocity [or mass velocity]; feedstock density, distillation curve, and chemical composition; hydrogen concentration and HRG circulation ratio; quantity of catalyst, quantity of free hydrogen formed; pressure and temperature in the system; and the yield and chemical composition of the reformate. These equations can be used to calculate the rate constants of reforming reactions in reactors with either a fixed or moving bed of catalyst. Examples of numerical calculations of these constants are given in Table 1. By using this method to process numerous versions of naphtha reforming over various catalysts, graphic relationships were obtained for the constants k 1 - k 4 as a function of the process temperature; these relationships are shown in Figs. 1 - 3 . Also shown for comparison are the analogous relationships for the process of reforming over an aluminosilicate catalyst of one of the earlier modifications. 16

An analysis of Eqs. (1) and (9), along with equations for calculation of the chemical equilibrium constant kel [3], shows that as the temperature is increased, the c o n s t a n t k I tends to decrease (see Table 1 and Fig. 1), and the constant k2 to increase. This circumstance may facilitate optimization of the process indexes in reforming naphtha cuts by the use of Eqs. (5)-(8).

REFERENCES
1.

2. 3. 4. 5.

Yu. M. Zhorov, Modeling of Physicochemical Processes in Petroleum Refining and Petrochemical Production [in Russian], Khimiya, Moscow (1978). G. V. Rabinovich et al., Nefiepererab. Neftekhim., No. 1, 25-27 (1980). A. A. Kuznetsov, S. M. Kagermanov, and E. N. Sudakov, Calculation and Design of Processes and Vessels in the Petroleum Refining Industry [in Russian], Khimiya, Moscow-Leningrad (1974). E. T. Denisov, Kinetics of Homogeneous Reactions [in Russian], Vysshaya Shkola, Moscow (1988). M. Vervorner et al., Chem. Tech., No. 516, 328-333 (1962).

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